Phosphiniminosulfoxonium compounds and process for preparing the same



United States Patent 3,524,881 PHOSPHINIMINOSULFOXONIUM COMPOUNDS AND PROCESS FOR PREPARING THE SAME Ted J. Logan, Colerain Township, Hamilton County, and

Terence W. Rave, Cincinnati, Ohio, assignors to The Procter & Gamble Company, Cincinnati, Ohio, a corporation of Ohio No Drawing. Filed Oct. 25, I966, Ser. No. 589,208

Int. Cl. C07c 145/00 US. Cl. 260551 6 Claims ABSTRACT OF THE DISCLOSURE The phosphiniminosulfoxonium salts and a process for preparing these salts are disclosed. The phosphiniminosulfoxonium salts are useful as emulsifying, fabric softening and antibacterial agents.

This invention relates to novel phosphiniminosulfoxonium salts which are emulsifying, fabric softening, and antibacterial agents. It further relates to a process for preparing these novel compounds.

The term phosphiniminosulfoxonium is used herein to denote a compound containing a [51 linkage, which linkage is explained hereinafter. Compounds containing this linkage are not known to have been described in the prior art.

There are several fabric softening agents which are commercially available and which are of much different chemical structure from the compounds of the present invention. Some of these commercially available softening agents, while effectively softening fabric thereby reducing or eliminating harsh feel, resist removal when the softened fabric is washed and upon continued reapplication can waterproof the fabric or garment to which they are applied. This waterproofing effect is undesirable es pecially in the case of, for example, towels, diapers, underwear, etc. Removable softening agents, such as certain of the compounds of the present invention, which after two washings of the fabric or garment to which they have been applied are more than 70% removed, are advantageous in that the tendency of the garments to which the agents are applied to become waterproofed is lessened, especially when compared to the softening agents which are commercially available.

It is, therefore, an object of this invention to provide r novel phosphiniminosulfoxonium salts which are effective as removable softening agents, that is, which after two washings of the fabric or garment to which they have been applied are more than about 70% removed.

It is a further object of this invention to provide novel r phosphiniminosulfoxonium salts which are effective as emulsifying agents and antibacterial agents.

It is another object of this invention to prepare phosphiniminosulfoxonium salts by reacting N-alkali-metal sulfoximines with trisubstituted phosphine dihalides or dipseudohalides.

According to this invention, it has been found that phosphiniminosulfoxonium salts having the following structural formula are effective as emulsifying agents, removable softening agents, and antibacterial agents:

X o G) T RR1R2P=N2SR3R4 wherein R and R are each radicals selected from the group consisting of aliphatic radicals containing from 1 to about 20 carbon atoms, phenyl, and substituted phenyl;

R R and R are each radicals selected from the group consisting of aliphatic radicals containing from 1 to about 4 carbon atoms, phenyl and substituted phenyl; and X is an anion which permits adequate solubility and hydrolytic stability of the salt. For an emulsifying agent, either R or R or both of these radicals is an aliphatic radical containing from about 12 to about 20 carbon atoms. For a removable fabric softening agent R and R are each aliphatic radicals containing from about 12 to about 20 carbon atoms and R R and R are each aliphatic radicals containing from 1 to about 4 carbon atoms. All of the above compounds are antibacterial agents.

The above structural formula and more particularly the [sP:N=s=1 linkage in this structural formula is a resonance structure. Thus, this structural formula represents the following structural formulas which are in resonance and in which R, R R R R and X are defined as above:

In these structural formulas R, R R R and R can each be of different chain lengths within the same compounds. The aliphatic radicals in this structural formula can be saturated or unsaturated and branched or straight chain. For example, these aliphatic radicals can be alkyl, substituted alkyl, alkenyl, and substituted alkenyl radicals. The term alkyl is used herein to include only saturated carbon chains. The term alkenyl is used herein to include carbon chains containing one or more double bonds.

The substituents in the substituted alkyl and substituted alkenyl radicals include, for example, chloro, hydroxy, and phenyl radicals. The substituents in the substituted phenyl radicals include, for example, methyl. ethyl, propyl, chloro, and hydroxy radicals.

The exact nature of the anionic portion of the above phosphiniminosulfoxonium salts is thought to be immaterial so far as the utility of these new compounds is concerned. Accordingly, virtually any organic or inorganic cation which permits adequate solubility of the phosphiniminosulfoxonium salts, i.e., a solubility of at least about 10 ppm. in water, and which permits hydrolytic stability of the salts, i.e., which provides stable anionic and cationic moieties upon solution in water, is suitable depending upon availability and cost factors. Thus, X in the above structural formula can suitably be, e.g., a halide anion such as chloride, bromide, iodide, or fiuoride anion; a sulfonate anion, such as methane sulfonate or p-toluene sulfonate anion; sulfate, nitrate, chlorate, and other anions, for example, fiuoroborate and hexachloroantimonate anions.

Preferably, the aliphatic radicals in the present phosphiniminosulfoxonium salts are alkyl radicals, and the anion, X is a halide, most preferably, chloride, bromide or iodide anion.

Useful phosphiniminosulfoxonium compounds, none of which are known to be described in the prior art, and, which are exemplary of those within the present invention, are set forth in Table I below wherein R, R R R R and X are applied in the structural formula set forth above. The utilities indicated for each particular compound in Table I are not necessarily exclusive.

TABLE I R R 1 R 2 R 3 R 4 X Utility 1 meth l Methyl Methyl Methyl MethyL..- 80 Antibacterial. E2gethy1i" Ethylm Ethyl .d Butyl 010;- Do. (3) pro yl Methyl. 3-10d0propenyL. (1 Do. (4) liydroxybutyl do Methyl..- D (5) octyL... Do. (6) decyl t Do. (7) dodeeyl (str ght) Dmulsiher.

h (8? t r ir i ecyl do v do Butyl Hexyl p-(CHQC IhSO O- Do. tetradecyl Butyl Buty1 Hydroxymethyl... Methyl... Br- Do. H (10) hexadceyl... MethyL. Methyl. MethyL E Softener, emulsifier. (11) oetadccyL. ....do .do "do Do. (12) oleyl... .do. 11 do leyl.. Do. (13) eicy1 3-hydrtixyp Dodecyl. Do.

peny th 1 Meth 1 d0 .do OctadeeyI.... Cl" Emulsrficr. p iiiengl P116115 1... Phcuyl ..do. Methyl 1- Antibacterial. (16) 3-phenylpropyl Methyl D0. (17) methyl -.go... 13g. (18) plmethylphcnyl n n 0 n W Softener, emulsifier.

(19) dodeeyl (tetrapropylene) 1 Where the valence of the anion is greater than 1, a number of cations equal to this valence are present in each salt molecule.

The emulsifying phosphiniminosulfoxonium salts of the present invention ordinarily can be used to produce oil-in-water emulsions that are stable for more than one hour, the weight ratio of emulsifier to oil phase generally ranging from about 1:1000 to about 3:1.

The antibacterial phosphiniminosulfoxonium salts of the present invention can be dissolved in water or other inert carrier in the range of about p.p.m. to about 1000 ppm. and the solution used for antibacterial, e.g., disinfecting, purposes.

The softener phosphiniminosulfoxonium salts of the present invention effectively soften fabric, for example, towels, thereby reducing or eliminating harsh feel. Moreover, they are removable softening agents, and after two washings of the fabric or garment to which they have been applied are more than 70% removed from the fabric or garment. This reduces the tendency of such fabric or garment to become waterproofed after multiple applications of softening agent and preserves the ability of towels, underwear, etc. to absorb moisture. Thus these salts are suitably used as active ingredients in fabric softener compositions.

The fabric softener compositions referred to above can be in the form of liquids, granular products, tablets, and in other forms.

For example, a liquid fabric softener composition can comprise from about 1% to about by weight of softening phosphiniminosulfoxonium salt and from about 85% to about 99% water. Such compositions also contain preferably from about 1% to about 50%, and more preferably from about 1% to about 10%, by weight of an alcohol containing from 1 to about 4 carbon atoms, such as, for example, ethanol or isopropanol, in place of an equal weight of water. This alcoholic component reduces the viscosity of the softener composition thereby causing it to be more readily pourable and also reduces the tendency of the composition to become a gel. This alcoholic ingredient also desirably acts as a freeze point depressant thereby reducing the possibility of the composition freezing during shipping whereby the compositions container is possibly ruptured. Thus, a preferred liquid fabric softener composition herein consists essentially by weight of from about 1% to about 15% phosphiniminosulfoxonium salt, from about 1% to about 50% alcohol, and from about 35% to about 98% water while an especially preferred liquid fabric softener composition herein consists essentially by weight of from about 1% to about 15% phosphiniminosulfoxonium salt, from about 1% to about 10% alcohol, and from about 75% to about 98% water. Optional ingredients for the present liquid fabric softener compositions include, for example, perfume, coloring agent, and up to about 1% or more of a nonionic detergent such as, for example, nonyl phenoxy polyoxyethylene ethanol, containing 5 to moles of ethylene oxide per mole of phenol, to help stabilize the composition.

These softener compositions are applied, for example, by the housewife to fabric during laundering. The housewife can cause the application of such a softener composition simply by adding it, for example, by pouring, into the rinse water which is present during the n'nse cycle of washing machine operation. For effective softening, the fabric softener composition is added to the rinse water in amount sulficient to provide a concentration of phosphiniminosulfoxonium salt in the rinse water ranging from about 10 p.p.m. to about 500 p.p.m. and preferably from about 25 p.p.m. to about 100 p.p.m.

Turning now to further uses of the present phosphiniminosulfoxonium salts, these compounds can be added as emulsifiers, removable softening agents, or antibacterial additives to various detergent compositions, and ordinarily comprise from about 1% to about 15% by weight of such detergent compositions. The detergent active in these detergent compositions is any detergent which is compatible with the phosphiniminosulfoxonium salt additive. Ordinarily, this detergent active is a nonionic, zwitterionic, or ampholytic synthetic detergent. The detergent active ordinarily comprises from about 5% to about by weight of these detergent compositions.

The above mentioned nonionic synthetic detergents can be broadly defined as compounds produced by the condensation of alkylene oxide groups (hydrophilic in nature) with an organic hydrophobic compound, which can be aliphatic or alkylaromatic in nature. The number of the hydrophilic or polyoxyalkylene radicals which are condensed with any particular hydrophobic group can be readily adjusted to yield a water-soluble compound having the desired degree of balance between hydrophilic and hydrophobic elements.

For example, a well-known class of nonionic synthetic detergents is made available on the market under the trade name Pluronic.- These compounds are formed by condensing ethylene oxide with a hydrophobic base formed by the condensation of propylene oxide with propylene glycol. The hydrophobic portion of the molecule, which, of course, exhibits water insolubility, has a molecular weight of about 1500 to 1800. The addition of polyoxyethylene radicals to this hydrophobic portion tends to increase the water solubility of the molecule as a whole, and the liquid character of the products is retained up to the point where polyoxyethylene content is about 50% of the total weight of the condensation product.

Other suitable nonionic synthetic detergents include:

(1) The polyethylene oxide condensates of alkyl phenols, e.g., the condensation products of alkyl phenols having an alkyl radical containing from about 6 to 12 carbon atoms in either straight chain or branched chain configuration, with ethylene oxide, the said ethylene oxide being present in amounts equal to 5 to 25 moles of ethylene oxide per mole of alkyl phenol. The alkyl substituent in such compounds can be derived from diiso- 5 butylene, octane, nonane, or polymerized propylene, for example.

(2) Those derived from the condensation of ethylene oxide with the product resulting from the reaction of propylene oxide and ethylene diamine-products which may be varied in composition depending upon the balance between the hydrophobic and hydrophilic elements which is desired. For example, compounds containing from about 40% to about 80% polyoxyethylene by weight and having a molecular structure of about 5000 to about 11,000, resulting from the reaction of ethylene oxide groups with a hydrophobic base, constituted of the reaction product of ethylene diamine and excess propylene oxide, said base having a molecular weight of the order of 2500 to 3000, are satisfactory.

(3) The condensation product of aliphatic alcohols having from 8 to 18 carbon atoms, in either straight chain or branched chain configuration, with ethylene oxide, e.g., a coconut alcohol/ ethylene oxide condensate having from 5 to 30 moles of ethylene oxide per mole of coconut alcohol, the coconut alcohol fraction of the condensate having from 10 to 14 carbon atoms.

(4) Trialkyl amine oxides and trialkyl phosphine oxides wherein one alkyl radical contains from about 10 to about 18 carbon atoms, from to about ether linkages, and from 0 to about 2 hydroxy groups and wherein the other two alkyl radicals each contain from 1 to about 3 carbon atoms, from 0 to about 2 ether linkages, and from 0 to about 2 hydroxy groups. Specific examples are dodecyl diethanol amine oxide and tetradecyl dimethyl phosphine oxide.

(5) Dialkyl sulfoxide detergents having the formula R -S R wherein R is a hydrocarbon group containing from about to about carbon atoms, from O to about 5 ether linkages, and from 0 to about 3 hydroxyl groups, there being at least one moiety of R which constitutes a carbon chain containing no ether linkages and containing about 10 to 18 carbon atoms, and wherein R is a short alkyl chain containing from about 1 to about 3 carbon atoms having O2 hydroxyl groups attached to said short alkyl chain. Specific examples of such sulfoxides are octadecyl methyl sulfoxide, dodecyl methyl sulfoxide, tetradecyl methyl sulfoxide, 3-hydroxytridecyl methyl sulfoxide, 3-methoxytridecyl methyl sulfoxide, 3-hydroxy-4-dodecoxybutyl methyl sulfoxide, Z-hydroxyundecyl methyl sulfoxide, 2-hydroxydecyl methyl sulfoxide, and 2-decoxyethyl-Z-hydroxyethyl sulfoxide.

Suitable zwitterionic detergents include detergents such as betaine and betaine-like detergents wherein the molecule contains both basic and acidic groups which form an inner salt giving the molecule 'both cationic and anionic hydrophilic groups over a broad range of water wash pH values. For example, suitable zwitterionic detergents include those having the formula R8 R l I R Z wherein R contains from about 10 to about 18 carbon atoms and from about 0 to about 5 ether linkages, wherein R and R are each selected from the group consisting of alkyl groups containing from 1 to about 3 carbon atoms, wherein R is selected from the group consisting of alkylene and hydroxy substituted al'kylene groups containing from 1 to about 4 carbon atoms, and wherein Z is selected from the group consisting of groups. Specific examples of such compounds are l-(hexadecyldimethylammonio) propane-B-sulfonate, l-(dodecyl- 6 dimethylammonio)butane-3-sulfonate, and l-(dodecyldimethylammonio) acetate. Some other common examples of these detergents are described in U.S. Pats. 2,082,275; 2,129,264; 2,217,846; 2,255,082; and 2,702,279.

The ampholytic detergents mentioned above are represented by detergents such as dodecyl-beta-alanine, N-alkyltaurines such as the one prepared by reacting dodecylamine with sodium iscthionate according to the teaching of U.S. 2,658,072, N-higher alkylaspartic acids such as those produced according to the teaching of U.S. 2,438,- 091, and the products soid under the trade name Miranol and described in U.S. Pat. 2,528,378.

The detergent compositions herein must not contain water-soluble alkaline detergency builder salts, either of the organic or inorganic types. This is because the phosphiniminosulfoxonium salts of the present invention are stable only in the pH range of 6 to 8 and are preferably maintained and employed at a pH of 7; the use of builder salts in the detergent composition ordinarily would provide a washing solution pH of from about 9 to about 12 under which conditions the present phosphiniminosulfoxonium salts tend to hydrolyze and lose their effectiveness. Thus, the detergent compositions herein must have a pH ranging from about 6 to about 8, preferably 7.

The present detergent compositions, when they are in the form of liquids, can optionally contain from about 1% to about 50%, preferably from about 1% to about 10%, by weight of an alcohol containing 1 to about 4 carbon atoms such as, for example, isopropanol or ethanol, to reduce the viscosity of the composition thereby causing it to be more readily pourable and also to reduce the tendency of the composition to become gel.

These detergent compositions can also contain many of the usual adjuvants, diluents, and additives, for example, antitarnishing agents (e.g., benzotriazole), anti-redeposition agents (e.g., alkali metal and ammonium salts of carboxymethyl cellulose), bacteriostatic agents, dyes or pigments, suds builders, suds depressors, and the like, without detracting from the advantageous properties of the composition.

Normally the organic detergent components, the phosphiniminosulfoxonium salt component, and the minor ingredients are incorporated into the composition prior to the conversion of the composition into final product form, e.g., detergent granules, flakes, etc., but they also can be added individually in the form of particles or as liquids.

Turning now to the process for preparing the abovedescribed phosphiniminosulfoxonium salts, these salts can be prepared by a process comprising reacting an N-alkalimetal sulfoximine with a trisubstituted phosphine dihalide or dipseudohalide.

The N-alkali-metal sulfoximine for use herein has the structural formula wherein R and R are defined as previously and M is an alkali metal selected from the group consisting of sodium, potassium, and lithium.

The trisubstituted phosphine dihalide or dipseudohalide for use herein has the structural formula wherein R, R and R are defined as previously and Y is selected from the group consisting of (1) halogens, for example, chlorine, bromine, and iodine atoms, and (2) pseudohalogens, for example, cyanide and azide moieties. Each Y can be the same or different in the same compound except that both Ys cannot be azide.

The above N-alkali-metal sulfoximines are reacted with the above trisubstituted phosphine dihalides or dipseudohalides in an inert atmosphere, for example, under argon, at a temperature ranging from about 0 C. to about 50 C. for a period of time ranging from about 0.5 hour to about 30 hours to provide essentially complete reaction. Room temperature is a preferred reaction temperature. Reaction times ranging from about 1 hour to about 20 hours are preferred.

A reaction solvent is employed in this process which is compatible with the above reactants and with the reaction product. This reaction solvent is preferably an aliphatic or aromatic hydrocarbon such as benzene, hexane, toluene, and the like.

The following equation represents a typical example of the reaction of this process The reactants in this process are not readily available commercially but can be prepared by a number of methods. For example, N-alkali-metal sulfoximines can be prepared by reacting a dialkyl sulfoximine with an aliphatic hydrocarbon alkali metal salt. This reaction is conveniently carried out in benzene reaction solvent without external heating at a temperature ranging from about C. to about 100 C. in an inert atmosphere, such as argon, with a reaction time ranging from about 0.5 hour to about 20 hours or more. Dialkyl sulfoximines are prepared by reacting dialkyl sulfoxides with hydroazoic acid in chloroform at 4050 C. with stirring for 16 hours; this preparation is described by H. R. Bentley, E. E. McDermott, and J. K. Whiteside, Proc. Royal Society, 138B, 265 (1951).

The trisubstituted dihalide or dipseudohalide can be conveniently prepared, for example, by reacting trisubstituted phosphines with a halogen or pseudohalogen. This reaction is carried out with no external heating, for example, in a solvent such as benzene and in an inert atmosphere such as argon. Reaction is substantially complete within about 10 minutes. The preparation of trisubstituted phosphines is described in the copending application of Hays, Ser. No. 461,669, filed June 7, 1965.

It is noted that the reactants in the above process for the production of phosphiniminosulfoxonium salts contain as anion producing constituents only halogens and the pseudohalogens, azide and cyanide. This limitation in the structure of the reactants is essential for the production of high yields of phosphiniminosulfoxonium salt since reactants containing, for example, oxygen-containing anionproducing constituents, produce high yields of by-products. Thus, this process is advantageously used directly only to produce phosphiniminosulfoxonium halides, azides and cyanides. However, the anions in the phosphiniminosulfoxonium salt products produced by this process can be converted to other anions by conventional techniques, for example, by means of an ion exchange column.

All percentages and parts herein are by weight unless otherwise specified. In all reactions herein where such reaction is carried out under an inert atmosphere, any inert atmosphere can be employed; for example, these reactions can be carried out in a vacuum or under inert gases such as argon, nitrogen, or helium.

The following examples are illustrative of the present invention and are not to be construed in any way as limiting the scope of the invention.

EXAMPLE I Preparation of dimethyldodecylphosphiniminodimethylsulfoxonium chloride 01 0 G9 1 C12H25(C]I3)2P:N'==S (CH3)2 Dimethylsulfoximine,

was prepared as follows: 31.2 grams (0.4 mole) of dimethyl sulfoxide was dissolved in 500 ml. chloroform. To this solution was added 120 ml. concentrated sulfuric acid. To the resulting mixture, stirred rapidly and under argon, was added 52 grams (0.8 mole) sodium azide over a twohour period. After this addition period, the mixture was stirred for 16 hours at 4045 C. Then, to this mixture was added 200 ml. water. The resulting mixture separated into two layers, an aqueous layer and a chloroform layer. Solid potassium hydroxide was added to the separated aqueous layer to adjust the pH to 8. The resulting mixture was filtered to remove potassium sulfate which had been formed as a result of the pH adjusting step. The filtrate was then evaporated to dryness in vacuo. The resulting While solid was extracted twice, each time with 100 ml. of methylene chloride. The combined extracts were dried over magnesium sulfate and then evaporated to yield a white solid. This white solid was distilled at approximately 1 mm. Hg at a pot temperature of 125 C. The fraction distilling at -98 C. was collected. This fraction crystallized to yield 22.0 grams of substantially pure dimethylsulfoximine.

A portion of this dimethylsulfoximine was converted to N-lithiodimethylsulfoximine,

as follows: In a ml. one-necked round-bottomed flask was placed 4.64 grams (50 mmoles) of the aboveprepared dimethylsulfoximine, and 50 ml. of benzene under an atmosphere of argon. A solution of dimethyl sulfoximine in benzene was then formed by means of vigorous stirring with a magnetic stirrer. To this solution at room temperature was added 35.75 ml. of 1.40 normal solution of n-butyllithium-hexane solution (50 mmoles of n-butyllithium) over a ten-minute period. The resulting milky white solution was stirred for two hours under argon without addition of external heat. The resulting solution containing N-lithiodimethylsulfoximine was used hereinafter without isolation or purification of the formed intermediate.

Dimethyldodecylphosphine dichloride was then prepared as follows: In a one-necked 1000 ml. round-bottomed flask equipped with a rubber cap and filled with argon was placed 11.60 grams (50.0 mmoles) of dimethyldodecylphosphine and 500 m1. of dry benzene. The formed solution was stirred vigorously while 1280 ml. of chlorine gas was injected into the capped flask. The reaction mixture was then stirred for one hour at room temperature. The resulting solution containing dimethyldodecylphosphine dichloride was used herein after without isolation or purification of the formed intermediate. The above dimethyldodecylphosphine was prepared by the method of Hays, previously referred to.

At this point the above-formed N-lithiodimethylsulfoximine solution was added to the above-formed dimethyldodecylphosphine dichloride solution. This addition was elfected over a 10-minute period with all compounds under argon. The resulting mixture was stirred or 16 hours with no external heating (the mixture was at 25 30 C.) to provide an insoluble white solid and a clear supernatant. This mixture was filtered. The solid was extracted two times, each time with 50 ml. of methyl cyanide, and the extracts were centrifuged to deposit lithium chloride. The centrifugate was then added to the filtrate, and the combined liquids were evaporated to dryness in vacuo to give a gummy white solid. Recrystallization of this solid from benzene-hexane (1:1 volume mixture) yielded 8.83 grams of dimethyldodecylphosphiniminodimethylsulfoxonium chloride. This compound is an effective emulsifier for oil-in-water emulsions and an effective antibacterial agent.

9 EXAMPLE 11 Preparation of dimethyloctadecylphosphiniminohexadecylmethylsulfoxonium chloride Hexadecylmethylsulfoximine,

was prepared as follows: 5.0 grams (17.35 mmoles) hexadecylmethylsulfoxide was dissolved in 50 ml. chloroform. To this solution was added 5.1 ml. concentrated sulfuric acid. To the resulting mixture, stirred rapidly and under argon, was added 2.21 grams (34 mmoles) sodium azide over a two-hour period. After this addition period the mixture was refluxed (at about 61 C.) for 16 hours. The mixture was then cooled to room temperature. To this mixture was added 30 ml. of water. The resulting mixture separated into two layers, an aqueous layer and a chloroform layer. The pH of the aqueous layer was adjusted to about 7.5 by the addition of solid potassium hydroxide to the mixture comprising both the water and chloroform layers; the pH of the chloroform layer became about 5.5. The chloroform layer was decanted. The aqueous layer was extracted two times, each time with 100 ml. of methylene chloride. These extracts were combined with the chloroform layer and the combined liquids were dried over sodium sulfate and then evaporated to yield a white solid. The white solid was recrystallized once from 1:1 by volume benzene-hexane to give 3.45 grams of hexadecylmethylsulfoximine.

This hexadecylmethylsulfoximine was converted to N- 1ithiohexadecylmethylsulfoximine,

as follows: In a 200 ml. one-necked round-bottomed flask was placed 3.43 grams (11.3 mmoles) of the above-prepared hexadecylmethylsulfoximine and 100 ml. benzene under an atmosphere of argon. A solution of hexadecylmethylsulfoximine in benzene was then formed by means of vigorous stirring with a magnetic stirrer. To this solution at room temperature was added 8.2 ml. of 1.36 normal solution of n-butyl-lithium-hexane solution (1 equivalent of n-butyllithium) over a give-minute period. The resulting solution was stirred under argon for three hours without addition of external heat. The resulting solution was stirred under argon for three hours without addition of external heat. The resulting solution containing N- lithiohexadecylmethylsulfoximine was used hereinafter without isolation or purification of the formed intermediate.

Dimethyloctadecylphosphine dichloride was then prepared as follows: In a one-necked 500 ml. round-bottomed flask equipped with a rubber cap and filled with argon was placed 3.50 grams (11.2 mmoles) dimethyloctadecylphosphine and 150 ml. of dry benzene. The formed solution was stirred vigorously While 279 ml. (11.3 mmoles) chlorine gas was injected into the capped flask. The reaction mixture was then stirred for one hour at room temperature. The resulting solution containing, dimethyloctadecylphosphine dichloride was used hereinafter without isolation or purification of the formed intermediate. The above dimethyloctadecylphosphine was prepared by the method of Hays, previously referred to.

At this point the above-formed N-lithiohexadecylmethylsulfoximine solution was added to the above-formed dimethyloctadecylphosphine dichloride solution. This addition was effected over a -minute period with all compounds under argon. The resultng mixture was stirred for 16 hours at a temperature ranging from -30 C.

(no external heating) to provide an insoluble white solid and a clear supernatant. The solid was recrystallized twice from a 1:1 by volume mixture of methyl alcohol and methyl cyanide to yield 1.79 grams of dimethyloctadecylphosphiniminohexadecylmethylsulfoxonium chloride. This compound is an effective and removable fabric softener.

Other phosphiniminosulfoxonium salts are prepared by the method of Example II if molar equivalents of other N-alkali-metal sulfoximines are substituted for the N- lithiohexadecylmethylsulfoximine in Example II and/or molar equivalents of other trisubstituted phosphine dihalides or dipseudohalides are substituted for the dimethyloctadecylphosphine dichloride in Example II. For example, N-sodiomethylpalmitoleylsulfoximine is reacted with dimethyltetrapropylenephosphinedibromide to produce the softener dimethyltetrapropylenephosphiniminomethylpalmitoleylsulfoxonium bromide, N-potassiodibutylsulfoximine is reacted with trimethylphosphine dicyanide to produce the antibacterial compound trimethylphosphiniminodibutylsulfoxonium cyanide, and N-lithioethylp-ethylphenylsulfoximine is reacted with dibutylphenylphosphinemonoiodidemonoazide to form an antibacterial mixture of dibutylphenylphosphiniminoethyl p ethylphenylsulfoxonium iodide and azide.

The halide and pseudohalide anions of the phosphiniminosulfoxonium salts formed in Examples I and II above can be converted to other anions by conventional ion exchange techniques. For example, the dimethyloctadecylphosphiniminohexadecylmethylsulfoxonium chloride formed in Example II can be converted to dimethyloctadecylphosphiniminohexadecylmethyl sulfoxonium nitrate or sulfate in this manner.

The following example illustrates a fabric softener composition containing the new phosphiniminosulfoxonium salts. This composition is applied to fabric as a water solution containing 50 ppm. phosphiniminosulfoxonium salt. When so applied these compositions provide effective softening and after two washings of the fabric or garment to which they have been applied, they are more than 70 removed.

EXAMPLE III A suitable liquid fabric softener composition contains:

Percent Dimethyloctadecylphosphiniminohexadecylmethylsulfoxonium chloride 5 Isopropanol 2 3,4,4'-trichlorocarbanilide l The condensation product of 9 moles of ethylene oxide with one mole of nonyl phenol 1 Color 0.003 Perfume 0.25 Water Balance Other new softening phosphiniminosulfoxonium salts, for example, any of the compounds listed in Table I and classified as softeners, can be substituted for the dimethyloctadecylphosphiniminohexadecylmethylsulfoxonium chloride in the above example to provide compositions which provide the removable softening effect.

The following examples illustrate light-duty liquid detergent compositions containing as a softening agent the softening phosphiniminosulfoxonium salts of this invention. These detergent compositions are suitable for cleaning and softening delicate clothing such as sweaters or underwear. In these examples the compositions have a pH of about 7.

EXAMPLE IV Percent Dimethyloctadecylphosphiniminohexadecylmethylsulfoxonium chloride 10 Dimethyldodecylamine oxide 35 Ethanol 10 Water 45 11 EXAMPLE V Percent Diethyldodecylphosphiniminobutyldodecylsulfoxonium sulfate l Dimethylhexadecylphosphine oxide 32 Ethanol Water 48 In the above Examples IV and V, other new phosphiniminosulfoxonium salts, for example, any of the compounds listed in Table I and classified as softeners, emulsifiers, or antibacterial agents can be substituted for all or part of the phosphiniminosulfoxonium salts in the above Examples IV and V to provide softening, emulsifying, or antibacterial etfects, respectively. Moreover, various other detergent actives can be substituted for the detergent actives in Examples IV and V, above. For example, betahydroxydodecylmethyl sulfoxide, lauryl alcohol condensed with 10 moles of ethylene oxide, nonylphenol condensed with 9 moles of ethylene oxide, dodecyl-beta-alanine, the sodium salt of N-dodecyl taurine, disodium N-dodecyl aspartate, and l-(hexadecyldimethylammonio)propane-3-sulfonate can replace the amine oxide and phosphine oxide detergent actives in Examples IV and V. The compositions are light-duty liquid detergents having removable softening properties. Moreover, these various detergent actives can replace the detergent actives in the compositions set forth in this paragraph wherein the phosphiniminosulfoxonium salts are added for emulsifying or antibacterial effect.

The previously described novel phosphiniminosulfoxonium salts also have utility as skin penetrating agents and as herbicides. Various of these salts are also wetting agents, detergents, solubilizing agents, gelling agents, and hydrotroping agents.

The foregoing description has been presented describing certain operable and preferred embodiments of this invention. Other variations will be apparent to those skilled in the art.

What is claimed is:

1. A phos'phiniminosulfoxonium salt having the structural formula wherein R and R are each radicals selected from the group consisting of alkyl radicals containing from 1 to carbon atoms; R R and R are each radicals selected from the group consisting of alkyl radicals containing from 1 to 4 carbon atoms; and X is an anion which permits a solubility of at least 10 parts per million in water and which permits hydrolytic stability of the salt.

2. The phosphiniminosulfoxonium salt according to claim 1 wherein R is an alkyl radical containing from 12 to 20 carbon atoms and X is an anion selected from the group consisting of chloride, bromide, iodide, fluoride, sulfonate, sulfate, nitrate, chlorate, fluoroborate, and hexachloroantimonate.

3. The phosphiniminosulfoxonium salt according to claim 2 wherein R is dodecyl, R R R and R are each methyl and X is chloride.

4. The phosphiniminosulfoxonium salt according to claim 2 wherein R R and R are each alkyl radicals containing from 1 to 4 carbon atoms and R is an alkyl radical containing from 12 to 20 carbon atoms.

5. The phosphiniminosulfoxonium salt according to claim 4 wherein R is octadecyl, R R and R are each methyl, R is hexadecyl, and X is chloride.

6. A process for preparing a phosphiniminosulfoxonium salt, said process comprising the step of reacting in an inert atmosphere, in an inert solvent, and at a temperature ranging from 0 C. to 50 C., (1) an N-alkali-metal sulfoximine having the formula 0 'I R3R4S- NM wherein R is a radical selected from the group consisting of alkyl radicals containing from 1 to 4 carbon atoms, and phenyl; R the radical selected from the group con sisting of alkyl radicals containing from 1 to 20 carbon atoms, and phenyl; and M is an alkali metal selected from the group consisting of sodium, potassium, and lithium; with (2) a compound having the formula RR R PY wherein R is a radical selected from the group consisting of alkyl radicals containing from 1 to 20 carbon atoms, and phenyl; R and R are each radicals selected from the group consisting of alkyl radicals containing from 1 to 4 carbon atoms, and phenyl; and Y is selected from the group consisting of chloride, bromide, iodide, cyanide, and azide, wherein both Ys in said compound are not simultaneously azide.

References Cited Appel et al.: Chem. Ber., vol. 99, 3108-17 (1966). Appel et al.: Zeitschrift fur Anorg. & Allg. Chemie, vol. 311, pp. 290-301 (1961).

HENRY R. JILES, Primary Examiner H. I. MOATZ, Assistant Examiner U.S. Cl. X.R.

ll7l39.5, 138.5; 2528.75, 107, 8.9; 260544; 424320 

